Reaction of glucopyranose polymers



hatented Aug. 7, 1951 WITH DROXIDE S SUBSTITUTED AMMONIUM HY- Kenneth M. Gaver, Esther P. Lasure, and Levi M. Thomas, Columbus, Ohio, assignors to The Keever Starch Company, Columbus, Ohio, a

corporation of Ohio Application August 1, 1947, Serial No. 765,370

12 Claims. 1

The inventions disclosed in this application relate to new compositions of matter and to new processes for the formation of such new compositions of matter. The new compositions of matter invented by us result from the chemical reactions of primary, secondary, tertiary of quaternary substituted ammonium hydroxides with carbohydrates and similar material. Examples of the substituted ammonium hydroxides are:

' (where each R may be any monovalent organic radical) The carbohydrate may be any aldehyde or ketone derivative of a polyhydric alcohol. The formula for such a carbohydrate is .with hydrogen of the most acidic of the carbohydrate (or similar material) hydroxyls and the remainder of substituted ammonium hydroxide is substituted so as to form a carbohydrate having a formula of where each G is either a hydrogen atom or any monovalent organic radical and where It may be any monovalent organic radical. The processes described herein illustrating our inventions are especially designed to produce such new products from carbohydrates.

The new compositions of matter produced from the reactions of quaternary bases with starches are good examples thereof. In the production of such new compositions of matter from the reaction of quaternary bases with starch, the new process comprises ordinarily a step of reacting starch with a quaternary base so as to produce a compound composed of an undetermined number of polymerized glucopyranose units all or most of which units will each have a general structural formula substantially as follows:

0 H HOCH H(CH) (CHOH) (HO ONRRRR) 47 0- where R, R, R" and R' may be the same or different monovalent organic radicals. To designate compounds conforming to the above formula we use the terms quaternary starchates which we define as follows: Quaternary starchate means and is used in this specification and in the claims hereof in the sense of the compound composed of an undetermined number of polymerized glucopyranose units wherein a quinquevalent nitrogen having four substituent organic radicals attached thereto is substituted for one of the hydrogen atoms of one of the several hydroxyl groups of the starch unit so as to form a polymerized compound which in fact is (or is at least analogous to) an alcoholate or ether of starch.

As used in this specification and claims we define carbohydrate to means any aldehyde or lretone derivative of a polyhydric alcohol and starchate to mean any compound composed of an undetermined number of polymerized glucopyranose units wherein one or more metallic or monmetallic atoms or organic or inorganic radicals are substituted for one or more of the hydrogen atoms of the several hydroxyl groups of the starch unit to form a polymerized compound which in fact is (or at least is analogous to) an alcoholate or ether of starch.

Prior to our inventions as disclosed herein a certain process has been discovered for the substitution of alkaline metals in the starch molecule which I will refer to hereinafter as the ammonia process starchate. As demonstrated in copending application Serial No. 694,328 of Kenneth M. Graver, Esther P. Lasure and Derk V. Tieszen and in Patent No. 2,513,135, issued to Kenneth M.

application Serial No. 694,328 and in said Patent 2,518,135 there is disclosed the formation of a monosodium starchate, other monoalkali starch ates and monometallic, monononmetallic and monoorganic derivatives thereof but as was demonstrated in said copending applications and as will be demonstrated hereafter herein, such starchates also differ from the amidogen starchates and from the quaternary base starchates described herein.

One of the objects of our invention is the provision of new and useful products from carbohydrates and similar materials.

A further object of our invention is the provision of new processes of forming such new and useful products.

A further object of our invention is the provision of new and useful products formed from starch.

A, further object of this invention is the provision of tetra-substituted ammonium hydroxide starchates and of new methodsv of synthesizing such compounds.

A; further object of our invention is the provision f new and useful processes for. forming various new products from starch.

Further objects andadvantages of the present invention will be apparent from the following descriptionfreferencebeing had 'to the accom: panying'drawings wherein a preferred form 01 embodiment of the invention is clearly shown.

In the drawings;

Fig. 1: illustrates methods of synthesizing the desired. products.

In saidcopending applications Serial No..69 l,328 and No. 7 7.313, now Patent No. 2,518,135, there are. disclosed; inventions, relating to monometallic starchates (both alkaliandnonalkali) to monononmetallic starchates, to, monoorganic starchates, and to hydrolysis products of such starch ates and, to; methods; for; their preparation. We have discovered that where a carbohydrate (or similar material), isreactedin a nonaqueous systern with aprimary, secondary,tertiary or quaternary ammonium hydroxide as illustrated above, at a temperature of from 80-81 C., a reaction occurs inwhichwateris evolved and the carbohydrate (or similar material) is condensed with the substituted; ammonium hydroxide to form a substituted. ammonium carbohydrate product. Specifically, for example, where starch is reacted in a nonaqueous solvent withquaternary base, at

a temperatureoffrom 80-8l C., a reaction occurs 4 and water is evolved, (comprising the hydrogen of the number two hydroxyl from the glucopyranoseunitof th starch and the hydroxyl of the, quaternary base) to form the substituted ammonium starchate.

TYPE OF CARBOHYDRATE USABLE Any typeof carbohydrate is usable as is any other compound having a hydroxyl group on the carbon adjacent to a, carbonyl or potentially carbonyl group. Similar reaction products have.

soLvENTs.

Any nonaqueous system is suitable. If a soli vent is used it preferably should be substantially nonaqueous. Any of the higher boiling alcohols may be used as solvents although we prefer to1uen and consider butanol as very useful. Ketones, ethers and other hydrocarbon solvents may be used. In some cases no solvent need be used at all. For example, starch and a quaternary n evidence indicating the formation of any derivative other than mono.

PRESSURE We observed no particular benefits or detriments derived from pressure reaction.

TIME The time factor undoubtedly has considerable influence on the reaction. However, prolonged reaction periods do not seem to produce better reactions than short vigorous reactions, Nemgical study hasbeen given to this variable;

aEMovAL or WATER Preferably the water formed by the reaction should be removed substantially; as formed as also should most of any other Water" present in the system (as for example water contained in the carbohydrate or in the solvent) One of th most practical methods of removing water is by distillation. For example, water forms an azeotrop with many of the useful solvents enabling us to distil the water originally present in the system and the water formed by the reaction with a portion of the solvent while retaining in the system the main body of the solvent inasmuch as the azeotrope boils below the boiling point-of the solvent as Well asbelow thev boiling point of water. V

The process. of removing water from the. reacting systems is disclosed and claimed in-ourcopending application Serial No, 24,628, filed May 1, 1948.

CHARACTER OFAMDJIONIUM HYDROIXIDE Where a quaternary baseis mixed with the carbohydrate at a temperature of -81? 0., little diffic'iiltyis experienced with the reaction. Where a tertiary base isused, greater-difficulty is experienced andthe difficulty'in inducing the reaction is increased asthe ionization constant isgreduced when using the. secondary and primary bases. It was found that an ionization constant of 2 10'- was verydesirable-inreactionsinvolving alkali hydroxides such as sodium hydroxide: with starch. However, with the quaternary bases'an ionization constant as low-aslflis verysatisfactory. Moreover, primary, secondarygand'tertiary bases with even lower ionization constants can be made to react under strongly dehydrating conditions which induce the removal ofathe Water as formedas, for example, by distillation or by the use of dehydrating agents? Wehave been unable to cause either ammonia-or unsubstituted ammonium hydroxide to react.

PROPERTIES. on THEEBODUCTS;

The products formedhydrolyze immediately but notcompletely in water. They are decomposed by acids. They, are subject to replacement of'the N(R4) group by'metals when're'acted with 'metallic halides as is shown in the following Equation 1. They are subject to replacement of the N(R4) group by nonmetals when reacted with nonmetallic halides as is shown in the following Equation 2. The N(R4) group also may be replaced by organic groups according to Equation 3 following:

(where a equals one or more; M equals any metal; D an inorganic nonmetal; R an organic group; and X is a halogen or similarly reacting group such as, for example, a nitrate, etc.)

MECHANISM OF THE REACTION The mechanism of the reaction proceeds along lines similar to those illustrated by the following equations:

(1) Addition C6H1cOs+R4NOH- CsHmOaHONRA (2) Dehydration CsI-I1oO-5.H0NR4 CsH905NR4+H2O EXAMPLES Example I 50 grams of corn starch 60 grams of benzyl trimethyl ammonium hydroxide 500 m1. of toluene Heat with agitation and slow distillation until 250 ml. of distillate have been collected. Filter on suction, wash with toluene and then with ether and then air dry. Water is evolved in this reaction. Air dry weight of product 82 grams (calculated 89 grams). This weight yield approximates that obtained in the sodium starchate reaction. Distillate is neutral.

Erample II 200 grams wheat dextrin 91 grams anhydrous tetramethyl ammonium hydroxide 900 ml. normal butanol This mixture was heated with vigorous agitation at boiling temperatures with distillation until 1000 ml. of distillate was collected. The moisture originally present and that liberated in the reaction was removed from the reaction mixture as the benzene azeotrope. At the end of the reaction period the reaction product is filtered on suction, washed with benzene then with ether and air dried. Air dry weight 282 grams. The product is a pale buff free-flowing powder.

It is to be understood that the above described embodiments of our invention are for the purpose of illustration only and various changes may be made therein without departing from the spirit and scope of the invention.

We claim:

1. A process of forming uniformly substituted nitrogen containing glucopyranose polymers which comprises mixing glucopyranose polymers with a substituted ammonium hydroxide at a temperature in the range of C. to C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

2. A process of forming a uniformly substituted nitrogen containing glucopyranose polymers which comprises mixing glucopyranose polymers with a tetra substituted ammonium hydroxide in the range of from 80 C. to 115 C. in a substantially nonaqueous system.

3. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a mono substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

4. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a di-substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

5. A process of forming a uniformly substituted nitrogen containing starchate which comprises the process of heating a tri-substituted ammonium hydroxide with starch at a temperature of from 80 C. to115 C. in a substantially nonaqueous system with provision for substantial removal of water formed by the reaction.

6. A process of forming a uniformly substituted. nitrogen containing starchate which comprises the process of heating a tetra-substituted ammonium hydroxide with starch at a temperature of from 80 C. to 115 C. in a substantially non-aqueous system with provision for substantial removal of water formed by the reaction.

7. A new composition of matter consisting of uniformly substituted glucopyranose polymers substantially all units of which have a formula of where R is a monovalent alkyl radical having not more than four carbon atoms, and where each R, R" and R is a substituent selected from the group consisting of hydrogen and monovalent alkyl radicals having not more than four carbon atoms.

8. A new composition of matter formed by the reaction of glucopyranose polymers in a substantially non-aqueous system at a temperature of about 81 C. to about 115 C. with a substituted ammonium hydroxide and consisting of uniformly substituted glucopyranose polymers substantially all units of which have a structural formula of where R is a monovalent alkyl radical having not more than four carbon atoms and where each R, R" and R' is a substituent selected from the group consisting of hydrogen and monovalent ass-awe "ualkyl "radicals having not more than :four :carbon -atoms.

. 9. Astarchate substantially .each unit of which has the general structural .formula of where each-R may be:any monovalent alkylradimore than fourearbon-atoms.

-11. A starchates'ubstantially eachunit of-whieh --has the general strueturalformula of "wheraeaeh'R-is a monovalent alkyl radical havi inganotmo're than four carbon atoms.

-12. Astarchate substantially each unitof-whi ch has the ,general structural formula of Where R is a monovalent alkyl radicalhariih'g not more than four carbon atoms. 7 KENNETH M. GAVER. ESTHERPPLASURE. LEVI M. THOMAS.

I REFERENCES CITED )7 The rfollowing references are ofsrecord 1n the :file :of this patent:

UNITED STATES PATENTS Number Name Date 1 ,986;88l Dreyfus- Jan. 8; 1935 

1. A PROCESS OF FORMING UNIFORMLY SUBSTITUTED NITROGEN CONTAINING GLUCOPYRANOSE POLYMERS WHICH COMPRISES MIXING GLUCOPYRANOSE POLYMERS WITH A SUBSTITUTED AMMONIUM HYDROXIDE AT A TEMPERATURE IN THE RANGE OF 80* C. TO 115* C. IN A SUBSTANTIALLY NONAQUEOUS SYSTEM WITH PROVISION FOR SUBSTANTIALLY REMOVAL OF WATER FORMED BY THE REACTION.
 8. A NEW COMPOSITION OF MATTER FORMED BY THE REACTION OF GLYCOPYRANOSE POLYMERS IN A SUBSTANTIALLY NON-AQUEOUS SYSTEM AT A TEMPERATURE OF ABOUT 81* C. TO ABOUT 115* C. WITH A SUBSTITUTED AMMONIUM HYDROXIDE AND CONSISTING OF UNIFORMLY SUBSTITUTED GLUCOPYRANOSE POLYMERS SUBSTANTIALLY ALL UNITS OF WHICH HAVE A STRUCTURAL FORMULA OF 